EP4126535B1 - Verfahren zur herstellung von coextrudiertem vernetztem polyolefinschaum mit polyamiddeckschichten - Google Patents

Verfahren zur herstellung von coextrudiertem vernetztem polyolefinschaum mit polyamiddeckschichten

Info

Publication number
EP4126535B1
EP4126535B1 EP21719807.6A EP21719807A EP4126535B1 EP 4126535 B1 EP4126535 B1 EP 4126535B1 EP 21719807 A EP21719807 A EP 21719807A EP 4126535 B1 EP4126535 B1 EP 4126535B1
Authority
EP
European Patent Office
Prior art keywords
polypropylene
layer
foam
polyethylene
ppr
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP21719807.6A
Other languages
English (en)
French (fr)
Other versions
EP4126535A1 (de
EP4126535C0 (de
Inventor
Pawel Sieradzki
Jesse Jude BALDWIN
Dan Ben-Daat
Kaitlyn Michelle Bock
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Plastics America Inc
Original Assignee
Toray Plastics America Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US16/836,229 external-priority patent/US11479016B2/en
Priority claimed from US16/836,389 external-priority patent/US11628648B2/en
Application filed by Toray Plastics America Inc filed Critical Toray Plastics America Inc
Publication of EP4126535A1 publication Critical patent/EP4126535A1/de
Application granted granted Critical
Publication of EP4126535B1 publication Critical patent/EP4126535B1/de
Publication of EP4126535C0 publication Critical patent/EP4126535C0/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/20—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of indefinite length
    • B29C44/22—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of indefinite length consisting of at least two parts of chemically or physically different materials, e.g. having different densities
    • B29C44/24—Making multilayered articles
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    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
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    • B29C44/36—Feeding the material to be shaped
    • B29C44/46—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length
    • B29C44/50—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length using pressure difference, e.g. by extrusion or by spraying
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers

Definitions

  • JP H05 500485 A discloses a core-foamed multilayer sheet with one or more polyolefin-based resin layers.
  • the polyolefin resin can be selected among others from various polypropylene, polyethylene, ethylene vinyl acetate copolymer and mixtures thereof.
  • US 2006/216535 A1 relates to a film which may comprise polyolefins and/or combinations of polyolefins and polyamides.
  • Crosslinked polyolefin foam can be used in various commercial applications including, but not limited to, a trim component in a vehicle interior such as a door panel.
  • a polyolefin foam to be used on a vehicle door panel the foam layer is typically first laminated to a film, fabric, or foil to create a bilaminate. This flexible bilaminate then needs to be combined with a hard substrate to make the panel.
  • thermoforming techniques such as negative vacuum forming (NVF) and positive vacuum forming (PVF), compression molding, and low pressure molding (LPM), among others.
  • NVF negative vacuum forming
  • PVF positive vacuum forming
  • LPM low pressure molding
  • One technique is to inject the polypropylene at the offal portion of the bilaminate. While this is generally effective in solving the foam shear and degradation issues within the mold cavity, it increases the cost to make the panel. Injecting at the offal requires the offal to be longer along at least one side of the mold. The offal along the injection side will then also contain the injected polypropylene. The cost of wasting the additional offal - which includes both the bilaminate and injected polypropylene - can be substantial. Also, the offal is not readily recyclable - further adding to the cost of this additional waste.
  • a trilaminate can be the same as an LPM bilaminate with a flexible homopolymer based TPO or TPE layer laminated to the "B" side of the bilaminate.
  • the TPO or TPE layer acts as a protective skin layer and/or a sacrificial skin layer between the foam and the polypropylene being injected.
  • TPO or TPE layer thickness can be substantial in relation to the overall bilaminate thickness which increases material costs.
  • a 2 nd lamination step is required which further increases the cost of the trilaminate.
  • the protective TPO or TPE layer is also prone to shear and degradation at the injection site.
  • Vehicle door panel manufacturers using an LPM technology commonly continue to inject the polypropylene at the offal portion of the trilaminate. While the quantity of offal required for this setup is less than using a bilaminate, it still requires more offal than would be needed if injecting directly into the mold cavity. The cost of wasting the additional offal - which includes both the trilaminate of and injected polypropylene - is substantial. Difficulty with recycling the offal adds further cost to this manufacturing technique
  • the multilayered structure can be laminated to a film, fabric, or foil to create a bilaminate.
  • the bilaminate can then be used in LPM applications and overcome the problems associated with traditional LPM bilaminates and trilaminates used to produce vehicle interior trim components.
  • the polyamide layer can act as a more effective protective layer (versus a TPO or TPE layer) to the polypropylene being injected.
  • a polyamide can be selected that is not only above the melting temperature of the polypropylene being injected, but also above the injection temperature.
  • the high melt temperature of the polyamide can ensure that the polyamide remains intact, providing a barrier that does not melt or sheer when in contact with the injected polypropylene - even at the injection point.
  • injecting in the offal region can become unnecessary, further reducing the cost of offal waste.
  • the polyamide cap layer can be substantially thinner than a TPO or TPE layer when appropriately chosen for the LPM process by being a non-sacrificial layer, thereby further reducing material costs.
  • the first layer may comprise at least 70 wt. % polypropylene, polyethylene, or a combination of polypropylene and polyethylene.
  • the second layer may be less than 1 mm.
  • the first layer may comprise additives in an amount of 1-20 wt. %.
  • the second layer may comprise additives in an amount of 1-10 wt. %.
  • the polypropylene may have a melt flow index of 0.1-25 grams per 10 minutes at 230°C, as measured according to ASTM D1238.
  • the polyethylene may have a melt flow index of 0.1-25 grams per 10 minutes at 190°C, as measured according to ASTM D1238.
  • an amount of chemical foaming agent in the first layer may be 3-15 wt. %.
  • the chemical foaming agent may comprise azodicarbonamide.
  • the ionizing radiation may be selected from the group consisting of alpha, beta (electron), x-ray, gamma, and neutron.
  • the coextruded structure may be irradiated up to four separate times.
  • the ionizing radiation may be an electron beam with an acceleration voltage of 200-1500 kV.
  • an absorbed electron beam dosage may be 10-500 kGy.
  • the ionizing radiation may crosslink the extruded structure to a crosslinking degree of 20-75%, as measured by the "Toray Gel Fraction Percentage Method".
  • foaming may comprise heating the irradiated structure with molten salt and radiant heaters or a hot air oven.
  • the density of the multilayer foam structure may be 20-250 kg/m 3 .
  • the multilayer foam structure may have an average closed cell size of 0.05-1.0 mm.
  • the multilayer foam structure may have a thickness of 0.2-50 mm.
  • the system, composition, or device When a system, composition, or device is described as “consisting essentially of” the listed components, the system, composition, or device contains the components listed, and may contain other components which do not substantially affect the performance of the system, composition, or device, but either do not contain any other components which substantially affect the performance of the system, composition, or device other than those components expressly listed; or do not contain a sufficient concentration or amount of the extra components to substantially affect the performance of the system, composition, or device.
  • a method is described as “consisting essentially of” the listed steps, the method contains the steps listed, and may contain other steps that do not substantially affect the outcome of the method, but the method does not contain any other steps which substantially affect the outcome of the method other than those steps expressly listed.
  • substantially free of a specific component, a specific composition, a specific compound, or a specific ingredient in various embodiments is meant that less than about 5%, less than about 2%, less than about 1%, less than about 0.5%, less than about 0.1%, less than about 0.05%, less than about 0.025%, or less than about 0.01% of the specific component, the specific composition, the specific compound, or the specific ingredient is present by weight.
  • substantially free of a specific component, a specific composition, a specific compound, or a specific ingredient indicates that less than about 1% of the specific component, the specific composition, the specific compound, or the specific ingredient is present by weight.
  • Described are methods of producing crosslinked, closed cell coextruded multilayer foam structures comprising at least a foam layer including polypropylene, polyethylene, or combinations thereof and at least a cap layer including polyamide.
  • the methods for producing a crosslinked, closed cell coextruded multilayer foam structure layer includes the steps of (a) co-extrusion, (b) irradiation, and (c) foaming.
  • foam compositions can be fed into multiple extruders to form an unfoamed, multilayer structure.
  • an "A" foam composition can be fed into one extruder and a "B" foam composition can be fed into a second extruder.
  • the method of feeding ingredients into the extruders can be based on the design of the extruder and the material handling equipment available.
  • Preblending ingredients of the foam compositions may be performed, if necessary, to facilitate their dispersal.
  • a Henshel mixer can be used for such preblending. All ingredients can be pre-blended and fed thru a single port in the extruder. The ingredients can also be individually fed thru separate designated ports for each ingredient.
  • Each extruder can deliver a steady amount of each composition into one or more manifolds followed by a sheeting die to create an unfoamed co-extruded multilayer sheet.
  • feed block manifolds There are two common methods for co-extruding materials: (1) feed block manifolds; and (2) multimanifolds within the die.
  • Elements of a feed block manifold can include: (a) inlet ports for the upper, middle, and lower layers; (b) a stream-lined melt lamination area that channels separate flow streams into one laminated melt stream inside the feed block; (c) an adapter plate between the feed block and the sheet die; and/or (d) a sheet die (similar to monolayer die), wherein the laminated melt stream enters the center of the die and spreads out along the manifold flowing out of the die exit as a distinct multilayer extrudate.
  • Layer thicknesses can be determined by the design of the manifold(s) and die.
  • an 80/20 feed block manifold can deliver compositions in approximately a 4:1 ratio when the speed and size of each extruder is matched accordingly. This ratio can be altered by changing, for example: (a) the relative extrusion speed between one extruder and another; (b) the relative size of each extruder; and/or (c) the composition (i.e., the viscosity) of the individual layers.
  • the thickness of the overall multilayer sheet can be controlled by the overall die gap. However, the overall multilayer sheet thickness can further be adjusted, for example, by stretching (i.e., "drawing") the melted multi-layer extrudate and/or flattening the melted multilayer extrudate through a nip.
  • the multilayer structures can include at least two layers made up of different compositions.
  • the multilayer structures include at least one layer made up of a foam composition and at least one layer made up of a non-foam cap composition.
  • the structure can be a B/A layered structure, B/A/B layered structure, B/A/C layered structure, or can have multiple other layers.
  • the multilayer structures can include additional layers such as tie layers, film layers, and/or additional foam layers among others.
  • a cap composition fed into the extruder can include at least one polyamide and a polypropylene, polyethylene, or a combination thereof.
  • a foam composition fed into the extruder can include a polypropylene, polyethylene, or a combination thereof.
  • Polyamides are polymers that contain an amide group (-CONH-) as a recurring part of the chain.
  • Polyamide includes, but is not limited to, aliphatic polyamide produced by either a condensation reaction of two bifunctional monomers or by ring-opening addition polymerization of cyclic chemical compounds.
  • the polyamide can be a homopolymer, copolymer, terpolymer, or a blend.
  • a semi-crystalline polyamide or polyamide blend is preferred over an amorphous polyamide or polyamide blend.
  • aliphatic polyamide homopolymer includes, but is not limited to, type 6, 11, 12, 46, 410, 56, 510, 511, 512, 513, 514, 66, 69, 610, 612, 613 1010, 1012, and 1212.
  • Commercially available aliphatic polyamide copolymer includes, but is not limited to, type 6/66, 6/69, 610/66 and 56/12.
  • Commercially available aliphatic polyamide terpolymer includes, but is not limited to, type 6/66/12.
  • Polypropylene includes, but is not limited to, polypropylene, impact modified polypropylene, polypropylene-ethylene copolymer, impact modified polypropylene-ethylene copolymer, metallocene polypropylene, metallocene polypropylene-ethylene copolymer, metallocene polypropylene olefin block copolymer (with a controlled block sequence), polypropylene based polyolefin plastomer, polypropylene based polyolefin elasto-plastomer, polypropylene based polyolefin elastomer, polypropylene based thermoplastic polyolefin, and polypropylene based thermoplastic elastomeric blend.
  • the polypropylene can be a high melt strength type.
  • the polypropylenes may be grafted with maleic anhydride.
  • Polyethylene includes, but is not limited to, LDPE, LLDPE (homopolymer, copolymer with butene or hexane or octene, terpolymer with butene and/or hexene and/or octene), VLDPE homopolymer, copolymer with butene or hexene or octene, terpolymer with butene and/or hexene and/or octene), VLLDPE (homopolymer, copolymer with butene or hexene or octene, terpolymer with butene and/or hexene and/or octane), HDPE, polyethylene-propylene copolymer, metallocene polyethylene, metallocene ethylene-propylene copolymer, and metallocene polyethylene olefin block copolymer (with a controlled block sequence), any of which may contain grafted
  • These polyethylenes may be grafted with maleic anhydride. These polyethylenes may also be copolymers and terpolymers containing acetate and/or ester groups and may be copolymer and terpolymer ionomers containing acetate and/or ester groups.
  • the polyamide in the non-foam cap composition fed into the extruder is 60-85 wt.-% polyamide, including 70-80 wt. % polyamide.
  • the amount polyethylene, polypropylene, or combination thereof in the non-foam cap composition fed into the extruder is 10-40 wt.-%, including 20-30 wt. % polyethylene, polypropylene, or combination thereof.
  • a foam composition fed into the extruder can include at least about 75 wt. % polypropylene, polyethylene, or a combination thereof, preferably at least about 80 wt. %, more preferably at least about 85 wt. %, and even more preferably at least about 90 wt. %.
  • the foam composition fed into the extruder can be at least about 70 wt. %, 80 wt. %, or 85 wt. %, polypropylene, polyethylene, or a combination thereof. In some embodiments, the foam composition fed into the extruder can be at most about 98 wt. %, 95 wt. %, or 90 wt. % polypropylene, polyethylene, or a combination thereof. In some embodiments, the foam composition fed into the extruder can be about 70-98 wt. %, 80-95 wt. %, or 85-90 wt. % polypropylene, polyethylene, or a combination thereof.
  • compositions Since a broad range of multilayer structures and foam articles can be created with the disclosed compositions, a broad range of polyamides, polypropylenes, and polyethylenes can be employed in the compositions to meet various in-process manufacturing requirements and commercial end use requirements.
  • polypropylene is an isotactic homopolypropylene.
  • Commercially available examples include, but are not limited to, FF018F from Braskem, 3271 from Total Petrochemicals, and COPYLENE TM CH020 from Phillips 66.
  • a non-limiting example of an "impact modified polypropylene” is a homopolypropylene with ethylene-propylene (EP) copolymer rubber.
  • the rubber can be amorphous or semicrystalline but is not in sufficient quantities to render the material any plastomeric or elastomeric properties.
  • a few non-limiting examples of commercially available "impact modified polypropylene” are TI4003F and TI4015F from Braskem and Pro-fax ® 8623 and Pro-fax ® SB786 from LyondellBasell.
  • Impact modified polypropylene-ethylene copolymer is polypropylene with random ethylene units and with ethylene-propylene (EP) copolymer rubber.
  • the rubber can be amorphous or semi crystalline, but is not in sufficient quantities to render the material any plastomeric or elastoplastomeric properties.
  • a non-limiting example of a commercially available impact modified polypropylene-ethylene copolymer is PRISMA ® 6910 from Braskem.
  • Metallocene polypropylene is metallocene syndiotactic homopolypropylene, metallocene atactic homopolypropylene, and metallocene isotactic homopolypropylene.
  • Non-limiting examples of "metallocene polypropylene” are those commercially available under the trade names METOCENE ® from LyondellBasell and ACHIEVE TM from ExxonMobil.
  • Metallocene polypropylenes are also commercially available from Total Petrochemicals and include, but are not limited to, grades M3551, M3282MZ, M7672, 1251, 1471, 1571, and 1751.
  • Metallocene polypropylene-ethylene copolymer is metallocene syndiotactic, metallocene atactic, and metallocene isotactic polypropylene with random ethylene units.
  • Commercially available examples include, but are not limited to, Lumicene ® MR10MX0 and Lumicene ® MR60MC2 from Total Petrochemicals, Purell ® SM170G from LyondellBasell, and the WINTEC ® product line from Japan Polypropylene Corporation.
  • Metallocene polypropylene olefin block copolymer is a polypropylene with alternating crystallizable hard “blocks” and amorphous soft “blocks” that are not randomly distributed - that is, with a controlled block sequence.
  • An example of “metallocene polypropylene olefin block copolymer” includes, but is not limited to, the INTUNE ® product line from the Dow Chemical Company.
  • Polypropylene based polyolefin plastomer POP
  • polypropylene based polyolefin elastoplastomer are both metallocene and non-metallocene propylene based copolymers with plastomeric and elastoplastomeric properties.
  • Non-limiting examples are those commercially available under the trade name VERSIFY ® (metallocene) from the Dow Chemical Company, VISTAMAXX ® (metallocene) from ExxonMobil, and KOATTRO TM (non-metallocene) from LyondellBasell (a butene-1 based line of plastomeric polymers - certain grades are butene-1 homopolymer based and others are polypropylene-butene-1 copolymer based materials).
  • VERSIFY ® metalocene
  • VISTAMAXX ® metalocene
  • KOATTRO TM non-metallocene
  • Polypropylene based polyolefin elastomer is both metallocene and non-metallocene propylene based copolymer with elastomeric properties.
  • propylene based polyolefin elastomers are those polymers commercially available under the trade names VERSIFY ® (metallocene) from the Dow Chemical Company and VISTAMAXX ® (metallocene) from ExxonMobil.
  • Polypropylene based thermoplastic polyolefin is polypropylene, polypropylene-ethylene copolymer, metallocene homopolypropylene, and metallocene polypropylene-ethylene copolymer, which have ethylene-propylene copolymer rubber in amounts great enough to give the thermoplastic polyolefin blend (TPO) plastomeric, elastoplastomeric or elastomeric properties.
  • TPO polymers are those polymers commercially available under the trade names THERMOR1JN ® and ZELAS ® from Mitsubishi Chemical Corporation, ADFLEX ® and SOFTELL ® from LyondellBasell, TELCAR ® from Teknor Apex Company, and WELNEX TM from Japan Polypropylene Company.
  • TPO can be produced via multi-stage polymerization (for example, ZELAS ® , ADFLEX ® , SOFTELL ® , and WELNEX ® ) or by blending (for example, THERMORUN ® and TELCAR ® ).
  • Polypropylene based thermoplastic elastomer blend is polypropylene, polypropylene-ethylene copolymer, metallocene homopolypropylene, and metallocene polypropylene-ethylene copolymer, which have diblock or multi-block thermoplastic rubber modifiers (SEBS, SEPS, SEEPS, SEP, SERC, CEBC, HSB and the like) in amounts great enough to give the thermoplastic elastomer blend (TPE) plastomeric, elastoplastomeric, or elastomeric properties.
  • SEBS thermoplastic rubber modifiers
  • Non-limiting examples of polypropylene based thermoplastic elastomer blend polymers are those polymer blends commercially available under the trade name GLS TM DYNAFLEX ® and GLS TM VERSAFLEX ® from Polyone Corporation, MONPRENE ® from Teknor Apex Company and DURAGRIP ® from LyondellBasell.
  • any of the above polypropylenes may also be a high melt strength (HMS) type.
  • HMS high melt strength
  • Polypropylene manufacturers employ various methods to strengthen the polymer in the melt phase.
  • polypropylene exhibiting long chain branching (LCB) can be identified as a high melt strength polypropylene.
  • high melt strength polypropylene are those polymers commercially available under the trade names DAPLOY ® from Borealis, AMPPLEO ® from Braskem, and WAYMAX ® from Japan Polypropylene Corporation.
  • mineral oil for example, mineral oil, PARALUX ® process oils from Chevron, etc.
  • LDPE and LLDPE are low density polyethylene and linear low density polyethylene, respectively.
  • Non-limiting examples of LDPE include at least those provided by Dow (e.g., 640I) and Nova (e.g., Novapol ® LF-0219-A).
  • Non-limiting examples of LLDPE include at least those provided by ExxonMobil (e.g., LLP8501.67) and Dow (e.g., DFDA-7059 NT 7).
  • Commercial LLDPE polymers are typically copolymers or terpolymers containing ⁇ olefins of butene and/or hexene and/or octene.
  • VLDPE and VLLDPE are very low density polyethylene and very linear density low density polyethylene and typically copolymers or terpolymers containing ⁇ -olefins of butene and/or hexene and/or octene.
  • Non-limiting examples of VLDPE and VLLDPE are commercially available under the tradename FLEXOMER ® from the Dow Chemical Company and particular grades of STAMYLEX ® from Borealis.
  • Metallocene polyethylene is metallocene based polyethylene with properties ranging from non-elastic to elastomeric.
  • Non-limiting examples of metallocene polyethylene are commercially available under the trade name ENGAGE TM from Dow Chemical Company, ENABLE TM and EXCEED TM from ExxonMobil, and QUEO ® from Borealis.
  • Metallocene polyethylene olefin block copolymer is a polyethylene with alternating crystallizable hard “blocks” and amorphous soft “blocks” that are not randomly distributed - that is, with a controlled block sequence.
  • An example of “metallocene polyethylene olefin block copolymer” includes, but is not limited to, the INFUSE TM product line from the Dow Chemical Company.
  • All of the above polyethylenes may be grafted with maleic anhydride.
  • Non-limiting commercially available examples are ADMER ® NF539A from Mitsui Chemicals, DuPont TM BYNEL ® 4104 from Dow, and OREVAC ® 18360 from Arkema. It should be noted that many commercial anhydride-grafted polyethylenes also contain rubber.
  • polyethylenes may also be copolymers and terpolymers containing acetate and/or ester groups.
  • the comonomer groups include, but are not limited to, vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate, glycidyl methacrylate, and acrylic acid.
  • Non-limiting examples are commercially available under the tradename DuPont TM BYNEL ® , DuPont TM ELVAX ® and DuPont TM ELVALOY ® from Dow; EVATANE ® , LOTADER ® , and LOTRYL ® from Arkema; ESCORENE ® , ESCOR ® , and OPTEMA ® from ExxonMobil.
  • the polypropylenes and polyethylenes listed above can be functionalized.
  • Functionalized polypropylenes and polyethylenes include a grafted monomer. Typically, the monomer has been grafted to the polypropylene or polyethylene by a free radical reaction.
  • Suitable monomers for preparing functionalized polypropylenes and polyethylenes are, for example, olefinically unsaturated monocarboxylic acids, e.g. acrylic acid or methacrylic acid, and the corresponding tert-butyl esters, e.g. tert-butyl (meth) acrylate, olefinically unsaturated dicarboxylic acids, e.g.
  • p-styrenesulfonic acid 2-(meth)acrylamido-2-methylpropenesulfonic acid or 2-sulfonyl-(meth)acrylate
  • oxazolinylcontaining olefinically unsaturated monomers e.g. vinyloxazolines and vinyloxazoline derivatives
  • epoxy-containing olefinically unsaturated monomers e.g. glycidyl (meth)acrylate or allyl glycidyl ether.
  • the most commonly commercially available functionalized polypropylenes are the ones functionalized with maleic anhydride.
  • Non-limiting examples are the ADMER ® QF and QB Series from Mitsui Chemicals, the PLEXAR ® 6000 Series from LyondellBasell, the DuPont TM BYNEL ® 5000 Series from Dow, and the OREVAC ® PP Series from Arkema.
  • the most commonly commercially available functionalized polyethylenes are also those functionalized with maleic anhydride.
  • Non-limiting examples are the ADMER ® NF and SE Series from Mitsui Chemicals, the PLEXAR ® 1000, 2000, and 3000 Series from LyondellBasell, the DuPont TM BYNEL ® 2100, 3000, 3800, 3900, 4000 Series from Dow, and the OREVAC ® PE, T, and some of the LOTADER ® Series from Arkema.
  • a polyamide film can be adhered to a polypropylene film by applying a tie layer of maleic anhydride grafted polypropylene between the film.
  • a catalyst for foaming agent decomposition may be used.
  • exemplary catalysts include, but are not limited to, zinc oxide, magnesium oxide, calcium stearate, glycerin, and urea.
  • the lower temperature limit for extrusion can be that of the polymer with the highest melting point. If the extrusion temperature drops below the melting temperature of the polymer with the highest melting point, then undesirable "unmelts" appear. Upon foaming, the extruded layer that was extruded below this lower temperature limit can exhibit uneven thickness, a non uniform cell structure, pockets of cell collapse, and other undesirable attributes.
  • the rougher surfaces of extrusion foamed articles can be generally caused by larger sized cells (when compared to the foams produced according to the present disclosure).
  • cell size and cell size distribution may not be as critical in most commercial applications, because surface roughness is a function of cell size, foams with larger cells can be less desirable than foams with smaller cells for applications requiring a smooth foam surface.
  • the cap can be thin and easily pliable when melted so as to not significantly hinder the expansion of the foamable layer(s) during the foaming step.
  • the cap's thickness, flexibility, and melt strength are among many physical properties that can hinder the foaming expansion of the other layer(s).
  • the thickness, flexibility, melt strength, and crosslinking percentage of the foamable layer(s) as well as the ultimate thickness and density of the foamed layers are also factors in whether the cap inhibits the expansion of the foamable layer(s).
  • a general guideline for maximum cap thickness is that it should be no more than about 20%, about 15%, about 10%, or about 5% of the overall coextruded unfoamed sheet. If the cap thickness is greater than about 20% of the overall coextruded unfoamed sheet, problems with the multilayered sheet curling, buckling, and folding onto itself may occur as the multilayered sheet is heated and foamed.
  • chemical crosslinking the crosslinks are generated with crosslinking promoters but without the use of ionizing radiation.
  • Chemical crosslinking typically involves using peroxides, silanes, or vinylsilanes. In peroxide crosslinking processes, the crosslinking typically occurs in the extrusion die. For silane and vinylsilane crosslinking processes, the crosslinking typically occurs post-extrusion in a secondary operation where the crosslinking of the extruded material can be accelerated with heat and moisture.
  • chemically crosslinked foam sheets typically exhibit primary surfaces that are significantly rougher than equivalent structures produced in the disclosed method.
  • the rougher surfaces of chemically crosslinked foamed articles can be generally caused by larger sized cells (when compared to the foams produced according to the present disclosure).
  • cell size and size distribution is not critical in most commercial applications because surface roughness is a function of cell size, foams with larger cells can be less desirable than foams with smaller cells for applications requiring a smooth foam surface.
  • the moldability of the resulting multilayered foam structure may be poor. Moldability is a desirable property when the multilayered foam sheet is used in thermoforming applications. Also, the unfoamed sheet may be softened by exothermic heat release upon exposure to the electron beam radiation such that the structure can deform when the exposure is too high. In addition, the polymer components may also be degraded from excessive polymer chain scission.
  • the radiation source may face the B layer of the coextruded, unfoamed multilayer sheet during irradiation. In some embodiments, the radiation source may face the A layer of the coextruded, unfoamed multilayer sheet during irradiation.
  • crosslinking can be performed so that the composition of the extruded structure may be crosslinked about 20 to about 75% or about 30 to about 60%, as measured by the "Toray Gel Fraction Percentage Method.”
  • tetralin solvent is used to dissolve non-crosslinked polyolefin components in a composition.
  • the non-crosslinked polyolefin material is dissolved in tetralin and the crosslinking degree is expressed as the weight percentage of crosslinked material in the entire composition.
  • the apparatus used to determine the percent of polymer crosslinking includes: 100 mesh (0.0045 inch wire diameter); Type 304 stainless steel bags; numbered wires and clips; a Miyamoto thermostatic oil bath apparatus; an analytical balance; a fume hood; a gas burner; a high temperature oven; an anti-static gun; and three 3.5 liter wide mouth stainless steel containers with lids.
  • Reagents and materials used include tetralin high molecular weight solvent, acetone, and silicone oil.
  • an empty wire mesh bag is weighed and the weight recorded. For each sample, 100 milligrams ⁇ 5 milligrams of the sample is weighed out and transferred to the wire mesh bag.
  • the weight of the wire mesh bag and the sample is recorded.
  • Each bag is attached to the corresponding number wire and clips.
  • the bundle (bag and sample) is immersed in the solvent.
  • the samples are shaken up and down about 5 or 6 times to loosen any air bubbles and fully wet the samples.
  • the samples are attached to an agitator and agitated for three (3) hours so that the solvent can dissolve the foam.
  • the samples are then cooled in a fume hood.
  • the samples are washed by shaking up and down about 7 or 8 times in a container of primary acetone.
  • the samples are washed a second time in a second acetone wash.
  • Suitable crosslinking promoters include, but are not limited to, commercially available difunctional, trifunctional, tetrafunctional, pentafunctional, and higher functionality monomers. Such crosslinking monomers are available in liquid, solid, pellet, and powder forms. Examples include, but are not limited to, acrylates or methacrylates such as 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylol propane trimethacrylate, tetramethylol methane triacrylate, 1,9-nonanediol dimethacrylate and 1,10-decanediol dimethacrylate; allyl esters of carboxylic acid (such as trimellitic acid triallyl ester, pyromellitic acid triallyl ester, and oxalic acid diallyl ester); allyl esters of cyanulic acid or isocyanulic
  • crosslinking promoters may be used alone or in any combination.
  • Divinylbenzene (DVB) a difunctional liquid crosslinking monomer
  • a suitable commercially-available DVB may include DVB HP by Dow.
  • the amount of crosslinking promoter in a foam layer composition can be less than or equal to about 5 PPR%, about 4 PPR%, about 3 PPR%, about 2.5 PPR%, about 2 PPR%, about 1.5 PPR%, or about 1 PPR% of the composition. In some embodiments, the amount of crosslinking promoter in a foam layer composition can be greater than or equal to about 0.5 PPR%, about 1 PPR%, about 1.5 PPR%, about 2 PPR%, about 2.5 PPR%, about 3 PPR%, or about 4 PPR% of the composition.
  • crosslinking promoter can be specific to DVB only. Other crosslinking promoters can be more or less efficient in crosslinking than DVB. Thus, the required quantity for another crosslinking promoter should be considered accordingly.
  • Crosslinking promoters can vary in crosslinking efficiency based on the ionizing radiation dosage, the polymers being crosslinked, the chemical structure of the monomer, the number of functional groups on the monomer, and whether the monomer is a liquid or a powder.
  • Crosslinks may be generated using a variety of different techniques and can be formed both intermolecularly, between different polymer molecules, and intramolecularly, between portions of a single polymer molecule.
  • Such techniques include, but are not limited to, providing crosslinking promoters which are separate from a polymer chain and providing polymer chains which incorporate a crosslinking promoter containing a functional group which can form a crosslink or be activated to form a crosslink.
  • foaming may be accomplished by heating the crosslinked multilayered sheet to a temperature higher than the decomposition temperature of the thermally decomposable blowing agent.
  • the foaming can be performed at about 200-260°C or about 220-240°C in a continuous process.
  • a continuous foaming process can be preferred over a batch process for production of a continuous foam sheet.
  • the foaming can be typically conducted by heating the crosslinked multilayered sheet with molten salt, radiant heaters, vertical or horizontal hot air oven, microwave energy, or a combination of these methods.
  • the foaming may also be conducted in an impregnation process using, for example, nitrogen in an autoclave, followed by a free foaming via molten salt, radiant heaters, vertical or horizontal hot air oven, microwave energy, or a combination of these methods.
  • the crosslinked multilayered sheet can be softened with preheating. This can help stabilize the expansion of the structure upon foaming, particularly with thick and stiff sheets.
  • the overall thickness of the multilayered foam sheet can be measured according to JIS K6767.
  • the thickness of the cap layer of the multilayered foam sheet can be measured using a microscope.
  • a small sample of the foam structure can be taken from the continuous foamed sheet.
  • the sample can be cut with an extra keen blade and the cross section of the sample viewed along the cut with a microscope.
  • a measurement can be performed with either a digital or traditional microscope.
  • a typical commercial digital microscope can have various software features to facilitate the thickness measurement.
  • a traditional commercial microscope can have a lens with measuring scales to facilitate the thickness measurement.
  • the density of the multilayered foam sheet can be defined and measured using section or "overall” density, rather than a "core” density, as measured by JIS K6767.
  • the multilayered foam sheets produced using the above described method can yield foams with a section, or "overall” density of about 20-250 kg/m3, about 30-200 kg/m3, or about 50-150 kg/m3.
  • the section density can be controlled by the amount of blowing agent and the thickness of the extruded structure. If the density of the multilayered foam sheet is less than about 20 kg/m3, then the sheet may not foam efficiently due to a large amount of chemical blowing agent needed to attain the density.
  • the density of the sheet is less than about 20 kg/m3, then the expansion of the sheet during the foaming step may become increasingly difficult to control. Furthermore, if the density of the multilayered foam sheet is less than about 20 kg/m3, then the foam may become increasingly prone to cell collapse. Thus, it may be difficult to produce a multilayered foam sheet of uniform section density and thickness at a density less than about 20 kg/m3.
  • the multilayered foam sheet may is not limited to a section density of about 250 kg/m3.
  • a foam having a section density of about 350 kg/m3, about 450 kg/m3, or about 550 kg/m3 may also be produced.
  • the foam sheet may have a density of less than about 250 kg/m3 since greater densities can be generally cost prohibitive when compared to other materials which can be used in a given application.
  • the foam layers produced using the above method may have closed cells.
  • at least 90% of the cells have undamaged cell walls, preferably at least 95%, and more preferably more than 98%.
  • the average cell size can be from about 0.05 to about 1.0 mm, and preferably from about 0.1 to about 0.7 mm. If the average cell size is lower than about 0.05 mm, then the density of the foam structure can typically be greater than 250 kg/m3. If the average cell size is larger than 1 mm, the foam may have an uneven surface. There is also a possibility of the foam structure being undesirably torn if the population of cells in the foam does not have the preferred average cell size. This can occur when the foam structure is stretched or portions of it are subjected to a secondary process.
  • the cell size in the foam layer(s) may have a bimodal distribution representing a population of cells in the core of the foam structure which are relatively round and a population of cells in the skin near the surfaces of the foam structure which are relatively flat, thin, and/or oblong.
  • the overall thickness of the multilayered polyolefin foam / polyamide cap sheet can be about 0.2 mm to about 50 mm, about 0.4 mm to about 40 mm, about 0.6 mm to about 30 mm, or about 0.8 mm to about 20 mm. If the thickness is less than about 0.2 mm, then foaming may not be efficient due to significant gas loss from the primary surface(s). If the thickness is greater than about 50 mm, expansion during the foaming step can become increasingly difficult to control. Thus, it can be increasingly more difficult to produce a multilayered polyolefin foam / polyolefin cap sheet with uniform section density and thickness.
  • a cap layer of the foamed, coextruded multilayer structure can have a thickness of about 0.0001-0.2 mm, about 0.001-0.15 mm, or about 0.05-0.1 mm. In some embodiments, a foam layer of the foamed, coextruded multilayer structure can have a thickness of about 0.5-6 mm, about 1-5 mm, or about 2-4 mm.
  • the desired thickness can be obtained by a secondary process such as slicing, skiving, or bonding.
  • Slicing, skiving, or bonding can produce a thickness range of about 0.1 mm to about 100 mm.
  • the thickness of the cap layer may be reduced upon foaming of the multilayered sheet. This can be due to the foamable layer(s) expanding and consequently stretching the cap layer(s). Thus, for example, if the multilayered sheet expands to twice its original area, the cap thickness can be expected to be about halved. If the multilayered sheet expands to four times its original area, the cap thickness can be expected to be reduced to about one-quarter of its original thickness.
  • the disclosed multilayer foam structures can be used in a variety of applications.
  • One such application is as an article produced via LPM.
  • a description of the multilayer foam structure as a trim component in a vehicle interior was provided.
  • the multilayer foam structure is not limited to vehicle door panels and can also be used in other vehicle interior parts such as door rolls, door inserts, door stuffers, trunk stuffers, armrests, center consoles, seat cushions, seat backs, headrests, seat back panels, knee bolsters, or a headliner.
  • thermoformed articles Another application is in thermoformed articles.
  • the structure can be heated to the melting point of the polyolefin foam layer and polyamide cap layer. Since most commercially available polyamides have a melting temperature greater than the polyolefin component(s) described in the disclosure, the multilayer foam structure can be heated to the melting point of the polyamide.
  • thermoformed article is an automobile air duct.
  • a closed cell foam structure can be particularly suited for this application due to its lower weight (when compared to solid plastic), its insulating properties that help maintain the temperature of the air flowing thru the duct, and its resistance to vibration (versus solid plastic).
  • a polyamide cap layer on the outside of the multilayered air duct can protect the air duct from contact with "under the hood” and vehicle interior liquids and greases that could negatively impact the functionality of the polyolefin foam.
  • the cap layer can also protect the foam layer from punctures and cuts during installation and during the life of the vehicle.
  • a firm polyolefin foam with polyamide cap can be suitable for an automobile air duct.
  • the multilayer foam structures can be laminates containing the multilayer foam and a laminate layer.
  • the laminate layer can be applied to a side (i.e., surface) of a foam layer opposite the cap layer.
  • the multilayer foam structure can, for example, be combined with a film and/or foil.
  • suitable materials for such layers include, but are not limited to, polyvinyl chloride (PVC); thermoplastic polyolefin (TPO); thermoplastic urethane (TPU); fabrics such as polyester, polypropylene, cloth and other fabrics; leather; and/or fiber layers such as non-wovens.
  • PVC polyvinyl chloride
  • TPO thermoplastic polyolefin
  • TPU thermoplastic urethane
  • fabrics such as polyester, polypropylene, cloth and other fabrics
  • leather and/or fiber layers such as non-wovens.
  • Such layers may be manufactured using standard techniques that are well known to those of ordinary skill in the art.
  • the multi-layer foam of the disclosure may include multiple other layers.
  • a layer may be joined to an adjacent layer by means of chemical bonds, mechanical means, or combinations thereof.
  • Adjacent laminate layers may also be affixed to each other by any other means including the use of attractive forces between materials having opposite electromagnetic charges or attractive forces present between materials which both have either a predominantly hydrophobic character or a predominantly hydrophilic character.
  • the disclosed structures of the present disclosure may be subjected to various secondary processes, including and not limited to, embossing, corona or plasma treatment, surface roughening, surface smoothing, perforation or microperforation, splicing, slicing, skiving, layering, bonding, and hole punching.
  • Table 3 provides irradiation and properties of the multilayer structure of Examples 1 and 2. Sections of the unfoamed sheet of Example 1 was irradiated under three separate dosages and further identified as Examples 1A - 1C. Sections of the unfoamed sheet of Example 2 was irradiated under seven separate dosages and further identified as Examples 2A - 2G.

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Claims (15)

  1. Verfahren zur Bildung einer mehrschichtigen Schaumstoffstruktur, wobei das Verfahren Folgendes umfasst:
    das Coextrudieren:
    einer ersten Schicht, die Folgendes umfasst:
    Polypropylen, Polyethylen oder eine Kombination von Polypropylen und Polyethylen;
    ein chemisches Treibmittel und
    einen vernetzenden Promotor in einer Menge von 0,5 -5 Gew.-% und
    eine zweite Schicht auf einer Seite der ersten Schicht, wobei die zweite Schicht Folgendes umfasst:
    60 - 85 Gew.-% Polyamid und
    10 - 40 Gew.-% Polypropylen, Polyethylen oder eine Kombination von Polypropylen und Polyethylen;
    das Bestrahlen der coextrudierten Schichten mit einer ionisierenden Strahlung und
    das Schäumen der bestrahlten coextrudierten Schichten.
  2. Verfahren nach Anspruch 1, wobei die erste Schicht mindestens 70 Gew.-% Polypropylen, Polyethylen oder eine Kombination von Polypropylen und Polyethylen umfasst.
  3. Verfahren nach einem der Ansprüche 1 - 2, wobei die Dicke der zweiten Schicht weniger als 1 mm beträgt.
  4. Verfahren nach einem der Ansprüche 1 - 3, wobei die erste Schicht Additive in einer Menge von 1 - 20 Gew.-% umfasst.
  5. Verfahren nach einem der Ansprüche 1 - 4, wobei die zweite Schicht Additive in einer Menge von 1 - 10 Gew.-% umfasst.
  6. Verfahren nach einem der Ansprüche 1 - 5, wobei das Polypropylen einen Schmelzflussindex von 0,1 - 25 Gramm pro 10 Minuten bei 230 °C, gemessen gemäß ASTM D1238, aufweist.
  7. Verfahren nach einem der Ansprüche 1 - 6, wobei das Polyethylen einen Schmelzflussindex von 0,1 - 25 Gramm pro 10 Minuten bei 190 °C, gemessen gemäß ASTM D1238, aufweist.
  8. Verfahren nach einem der Ansprüche 1 - 7, wobei die Menge des chemischen Treibmittels in der ersten Schicht 3 - 15 Gew.-% beträgt.
  9. Verfahren nach einem der Ansprüche 1 - 8, wobei das chemische Treibmittel Azodicarbonamid umfasst.
  10. Verfahren nach einem der Ansprüche 1 - 9, wobei die ionisierende Strahlung ausgewählt ist aus der Gruppe bestehend aus Alpha, Beta (Elektron), Röntgen, Gamma und Neutron.
  11. Verfahren nach einem der Ansprüche 1 - 10, wobei die coextrudierte Struktur bis zu vier Mal getrennt bestrahlt wird.
  12. Verfahren nach einem der Ansprüche 1 - 11, wobei es sich bei der ionisierenden Strahlung um einen Elektronenstrahl mit einer Beschleunigungsspannung von 200 - 1500 kV handelt, wobei die absorbierte Dosierung des Elektronenstrahls vorzugsweise 10 - 500 kGy beträgt.
  13. Verfahren nach einem der Ansprüche 1 - 12, wobei die ionisierende Strahlung die extrudierte Struktur bis zu einem gemäß der Beschreibung gemessenen Vernetzungsgrad von 20 - 75 % vernetzt.
  14. Verfahren nach einem der Ansprüche 1 - 13, wobei
    i) das Schäumen ein Erwärmen der bestrahlten Struktur mit geschmolzenem Salz und Strahlungsheizkörpern oder einem Heißluftofen umfasst
    und/oder
    ii) die Dichte der mehrschichtigen Schaumstoffstruktur 20 - 250 kg/m3 beträgt.
  15. Verfahren nach einem der Ansprüche 1 - 14, wobei die mehrschichtige Schaumstruktur eine Dicke von 0,2 - 50 mm aufweist.
EP21719807.6A 2020-03-31 2021-03-26 Verfahren zur herstellung von coextrudiertem vernetztem polyolefinschaum mit polyamiddeckschichten Active EP4126535B1 (de)

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US16/836,229 US11479016B2 (en) 2020-03-31 2020-03-31 Coextruded crosslinked polyolefin foam with polyamide cap layers
US16/836,389 US11628648B2 (en) 2020-03-31 2020-03-31 Method of making coextruded crosslinked polyolefin foam with polyamide cap layers
PCT/US2021/024485 WO2021202309A1 (en) 2020-03-31 2021-03-26 Method of making coextruded crosslinked polyolefin foam with polyamide cap layers

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EP4126535C0 (de) 2025-08-20
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WO2021202307A1 (en) 2021-10-07
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